Process of making alkyl chlorides



Nov. 10 1925. 1,560,625

w. R. WEBB PROCESS OF'IAKIIIG ALKYL GHLURIDES Filed July 18 1924 William,A E.. W'. W @XW Patented Nov. 1o, 1925. 1,560,625

UNITED STATES PATENT OFFICE.

Application led July 1l, 1924. lex-lll lo. 728,081.

To all whom it may com-rm: forni of the usual U-tuhe containing mer- 55 I le it known that. l. Yunnan R. 'unn, a cury. The tuhc. l0 and extension 7 may eoncitizen of the United States of America. reveniently he located in a removable closure siding at Rochester. in the county of Mon- 12 for t ie reaction vessel 8.

roc and Slate of New York, have invented First., 100 parts of anhydrous aluminum certain new and useful Improvements in chloride are charged intothc reaction v- Processes of Making Alkyl Chlorides, of sel 8. Then a mixture of equal parts of which the following is n full, clear, and exolefin gas, say ethylene, and hydrogen chloact lspecileation. ride is admitted to the reaction vessel under l0 Thisl invention relates to a process of makslight pressure until the gauge indicates a ing alkyl chlorides. One object of the inpressure equivalent to 2 of mercury, valve 05 rention is to provide a new process of mak- 4 being next closed to shut oli' the supply of in;Y one or more alkyl chlorides hy uniting gases. Ordinary room temperature may he one or more olclins and hydrogen chloride. employed, An action takes luce, which l5 Other olijccts will hereinafter appear. This appears to be an absorption ofp the roduct application is a continuation in part of my of the reaction in the aluminum eliloride, 70 application Serial No. 515347. filed Nov. 1G, although I do not wish to be restricted to a 1021, for process of making ethyl chloride. particular theory.

ln thc accompanying drawing Figs. 1 and As the reaction proceeds the pressure de- 2 are diagrammatic sectional views of ex creases and finally a vacuum is produced.

amples of apparatus in which my process lVhen this amounts to the equivalent of l 75 muy he carried out. of mercury, the valve 4 may he cautiously I have found that hydrogen chloride and opened and the mixed gases then slowly adolcfins react in the pwsenee of aluminum mittcd until the pressure in the. reaction veschloride to form substantial amounts of sel again rises to that of 2" of mercury. As

ulkvl chlorides. The ingredients are prefthe reaction proceeds, the aluminum chloride cra ly substantially anhydrous. Moreover heats up slightly and finally ma change in the preferred forms of my invention I its characteristic appearance to t at of a employ those olcfins which arc gaseous or thick plastic mass.

30 can be readily changed into the gaseous "hen the reaction proceeds by ascries of or vaporous state: so that the reaction can steps until the pressure changes do not: in-

he brought about while they are in that diente u sllfllcient further reaction or abstate. The fluid oletns (gaseous or liquid sorption, then vulve 41, which has previously atrooln temperature) are especially useful. heen opened, is closed, valve 4 is o cned and Since ethylene and octylene are typical, I valveV is opened to a wash hotte 13 conshall refer to them in the following extaining water. Tube 14 leading from the 90 amples, but it will be understood that: the wash bottle passes into a condenser 15 conother Huid membeis of the olefin series can taining*- a refrigeratiug mixture. The rebe used alone or mixed, due allowance heaction vessel 8' is then heated to approxiing malle, of course, for their different boilmately the boiling point of water-that is,

ing points. overa boiling water hath. The gases pass- 5 Referring to Fig. 1, dry ethylene, or ing ell' from the. heated aluminum chloride other gaseous olefin or a mixture of such mass enter the extension 7 and pass along olefins, enters by tube 1 and substantially tube 3 uml out: the side tube ."i through the dry hydrogen chloride enters uy tube 2 into 1Water wash bottle 13 and thence through the mixin pipe 3 controlled hy valves 4 pipe 14 to the condenser l5. With the con- 100 and 4l. rom pipe 3 extends u lateral pipe denser at a proximately 0 C., the alkyl 5 controlled by a. valve 6. A vertical extenchloride (etliyl chloride where ethylene is sion 'i' of pipe 3 enters the reaction vessel 8, used) will condense therein. It muy be rc extenda well toward the bottom thereof or moved from the condenser through an)r snitprefcrablgy above the top of the substantially able exit 16, controlled by valve 17.

anhydrous aluminum chloride 9. Tube 10 l'Vhere the olefin to be treated is a liquid leads from the vessel 8 to a pressure gaune at room temperature it is desirable to gusfy il which is shown conventionally in t e or vaporize it and effect the reaction while it is in such state. Referring to Fi 2 I shall describe the production of octy ch o ride, bci-nunc this is typical of the liquid olelins. but it will be understood that the other liquid oletins or mixtures can he likenisr treated in a similar manner.

Dry hydrochloric ucid gas enters into tube 18 controlled by stop cock l0, thi` tube I8 passing into mntniner 2l below Ihr level of the octylriie 2U in the bottom thereof, The container :ll is heated by any suitable means to facilitate the vaporizing of the octilcuc. Thus-. hy way of illustration, l have shown un oil hath '22 lu-iitcd hy a burin-r III. While the temperature of the orlvlene muy lul kept ul its boiling ioiiit, it is prefrriible to koop it somewhat iolow that point in order to control the pmcess beller, say 5 C., below llic boiling point. The steady stream of substantially anhy- 'llruiis hydrochloric uuid gas liiilililes through the heated octyll-ne und is thoroughly mixed with the vapors of the octylene in llie upper part of container 2l.

The mixed gum-s thi-ii pus-s through ipc 24, tothc'reaction rliiiuihcr 25, in whicli is located the catalytic material. This is pre fercbly anhydrous aluminum chloride. Any of the known expediente for giving a large surface to catalysts may be used, such us forming or sublining the aluminum chloride on to fragments of anv ini-.rt material, such as quartz, glues1 and the like. The reaction chamber 25 is kept at ii temperature Sudicicnt to irevent substantial condensation of the octylene, iis such. l'n other words, it muy be kopt roughly 25 C., above the hollincr point of the olefin. The reaction temperature will thus be about 150 C., in the case of oct Iene. 'lhe reaction chamber 25 is sullicicut y long to ell'ect a substantial reaction, having in view the contact area of the catalyst 2G. By way of illustration, I have shown the heating means for the reaction chamber or tubi` 25 to comprise a surrounding air bath 27 heated by burners 28.

The reaction may be conducted intermittently. say until the level of the octylene in container' 2l approaches the lower end of tube 1li: or it may be curried on continu onsly, new batches of the oleln being charged in the container ill through tube 32 controlled b stop cock 33.

The vapors rom reaction chamber 25 pass through nny suitable condenser 29 into collecting vessel 30. Preferably the latter con tains a suitable separating fluid, such :is water, 34. Since it is preferable to pass the gases thiough the reaction chamber 25 at a velocity which does not admit of com lete conversion of the olefin, the unchanged o efin, such as octylene, floats on top of the Water. The octyl chloride which is formed also floats on the water, together with am' polymerized hydrocarbons which may he lorinetl by intox-molecular coiuhinnlion of the olclns themselves. Any uncmnbined hydrochloric acid tends to dissolve in the water.

lly decuutiiig olf the oily layer of olefin,

alkyl chloride, and polynu-.rized li drocarbons und then washing them witi water a. Hubstantiull complete removal of any residual liydroc iloric acid can be effected. The )rushed oily mixture is then separated into its constituents by un preferred purilicntion method., say by flraetional distillation. lt the lutter procedure is i-=u-c of uctyl chloride, fractions boiling he iii-ecu 150 C. and 205 C. are selected. lhvu these are still further se|mraled by thv usual iroccdurc. Less po yniersation of the olelin -vapors mio complex liydrocarlmns takes place when mi excess of hydrochloric acid is present. Such an exceas is, therefore, maintained in the preferred forni of in invention. It is mm1-. easily effected if tie temperature of the liquid olelin in vessel 21 be kept considerably below its boiling point. I have, for example, been able to cai-ry out the reaction und lese-:en the polymerization of the oleln, especially in the case of octylene, by lower ing the tem erature of the liquid 20 even to 60 C. is materially lowers the vapor tension above the liquid; and con uently ilus How of substantially aah drous iydrouliloiic acid s through i )e 8 t0 the upper part of vc 2l is rendi y cpt high enough to insure un excess of the acid.

Having thus described my invention, what l claim as new and desire to secure by Letteiu Patent. is:

l. The process which comprises the step of reacting upon un olefin with hydrogen chloride in the resence of aluminum chloride until an algyl chloride is produced.

2. The process which comprises the step of reactin upon a substantiall anh drous olefin witi substantially anhy roue ydrogen chloride in the presence of substantially anhydrous aluminum chloride until an alkyl chloride is produced.

3. The process which com rises the step of reacting upon an olefin, wllich is fluid at loom temperature, with hydrogen chloride under the influence of un anhydrous aluminum chlorid until an alkyl chloride is produced;

4. The process which comprises the step of reacting upon ethylene with hydrogen chloride in the presence of aluminum chloride until ethyl chloride is produced.

5. The process which comprises the step of reacting upon substantially anhydrous ethylene with substantially anhydrous hydro en chloride in the presence of Substantial v anhydrous aluminum chloride until ethylene chloride is produced.

6. The process which comprises the step of reacting upon substantially anhydrous adopted iu the ethylene with substantially anhydrous hydro n chloride in the presence of substantial y' anhydrous aluminum chloride, the

ressure of said gases being diminished during such step.

The process which comprises the steps of repeatedly reactin on substantially anhydrous ethylene wit substantially anhydrous hydrogen chloride in the presence of substantially anhydrous aluminum chloride, the pressure being raised at the start of each repetition.

8. The process which comprises the steps of reacting on ethylene with hydrogen chloride in the presence of aluminum chloride until ethyl chloride is generated on said aluminum chloride, and removing and collectin said ethyl chloride.

9. he process which comprises the steps of reacting upon substantially anhydrous ethylene with substantially anhydrous hydro en chloride in the resence of substantialy anhydrous aluminum chloride until ethyl chloride is enerated on said aluminum chloride, an then removing and coltecting said ethyl chloride.

10. The process which comprises the steps of bringin a mixture of substantially anhydrous ethy ene and substantially anhydrous hydrogen chloride into contact with substantially anhydrous aluminum chloride until ethyl chloride is formed on said aluminum chloride` und then distilling off the said ethyl chloride and purifying and condensin the same.

igned at Rochester, New York, this 12th day of July, 1924.

WM. R. WEBB.

ethylene with substantially anhydrous hydrogen chloride in the resence of substantially anhydrous alumlnum chloride, the pressure of said gases being diminished durmg such step.

7. The process which comprises the steps of repeatedly reacting on substantially anhydrous ethylene with substantially anhydrous hydrogen chloride in the presence of substantially anhydrous aluminum chloride, the pressure being raised at the start of each repetition.

8. The process which comprises the steps of reacting on ethylene with hydrogen chloride in the presence of aluminum chloride until ethyl chloride is generated on said aluminum chloride, and removing and collecting said ethyl chloride.

9. The process which comprises the steps of reacting upon substantially anhydrous ethylene with substantially anhydrous hydrogen chloride in the resence of substantially anhydrous aluminum chloride until ethyl chloride is generated on said aluminum chloride, and then removing and coltecting said ethyl chloride.

10. The process which comprises the steps of bringin a mixture of substantially anhydrous ethy ene and substantially anhydrous hydrogen chloride into contact with substantially anhydrous aluminum chloride until ethyl chloride is formed on said aluminum chloride` and then distilliug oti' the said ethyl chloride and purifying and condensing the same.

Signed at Rochester, New York, this 12th day of July, 1924.

WM. R. WEBB.

Certificate of Correction.

It is hereby certified that Letters Patent No. 1,560,625, granted November 10, 1925, upon the application of William R. Tehh` of Rochester, New York. for an improvement in Processes of Making Alhyl Chlorides. were erronmusly issued to Carbide & Carbon (`hculirals Corporation, a Corporation of New York. Whereas said Letters lntcut should have heen issued hy direct and mcsnc assignments of one-half t [fast/mm. Kodak 'mnprmy. of [faciles-IM. il'. l'..

0f New York, and one-half fo Carbide d" (far/ou ('/zcluim/s ('w/mrnfimf. 1 ('m'- poration. of New York. as shown hy the records of assignments iu this oflice: and that the said Letters Patent should he read with this correction therein that the same may conform to the record ot the case in the Patent ()iice.

Signed and sealed this 15th day of December, A. I). 1925.

[SEAL] WM. KNNAX, .loting (lonwrz'ssioucr of Puffo/ifs.

Certiicate of Correction.

1t is hereby certified that Letters Patent No. 1,560,625, granted November 10, 1925, upon the application of VVllnm R.. Webb, of Rochester. New York. for an im rovement, in Processes of Makingv Alkyl (hloridesf were erronoongly issued to Carbide & Carbon Chemicals Corporationl` a. Corporation of Now York, whereas said Letters Potent should havo been issued hy direct and incisnc assignments of mw-half to Eastman Kodak (bmpmiy, of [techn/M Y.. n ('o/-l/mwfim: 0f New York, and one-half fo Carbide d'- (fori/0u ('zemf'a/.w Porpora/inn. n ('olporation of New York, as shown by the records of assignments in this oftice: and that, the said Letters Patent should be read with this correction thm-cin that the same may conform to the record of the case in the Patent; Ottico.

Signed and sealed this 15th day of December, A. D. 1925.

[SEAL] WM. A. KTNXAX,

Acting (tommssz'ovlm' of mcnfs. 

